Process for dyeing blends of cellulose and polyester fibers with reactive and disperse dyes



United States Patent F 3 331,654 PROCESS FOR DYEIN G BLENDS OF CELLULOSEAND POLYESTER FIBERS WITH REACTIVE AND DISPERSE DYES Hans Husy, Basel,Switzerland, assignor to Sandoz Ltd.

(also known as Sandoz A.G.), Basel, Switzerland No Drawing. Filed Dec.12, 1963, Ser. No. 329,969 Claims priority, application Switzerland,Dec. 17, 1962,

14,806/62; Dec. 20, 1962, 14,970/62; Dec. 28, 1962,

carried out at temperatures above 100 C. with the addition of not morethan 5 grams of a basic fixing agent per liter liquor and in thepresence of at least one neutral salt.

The natural celluloses which come into consideration for the processare, e.g., cotton, linen, hemp, jute and ramie. The term regeneratedcellulose refers to viscose rayon in the filament and staple fiberforms'and to cuprammonium rayon. Filaments and fibers of thesematerials, as well as fiber fleeces, woven and knitted fabrics and othertextile materials made from them, can be dyed by the new process, whichbelongs to the group of exhaustion dyeing processes. The filaments orfibers are dyed as loose mixtures with polyester fibers, in particularthose made from hydrophobic polycondensation products of terephthalicacid and glycols or 1,4-bis (-hydroxymethyl)- benzene, or in the form ofblended fabrics of cellulosic and polyester fibers. The dyebath containsreactive dyes for the natural or regenerated cellulose and disperse dyesfor the polyester fiber present in the mixture.

In the present context reactive and disperse dyes which are stable toalkalis at temperatures above 100 C. are understood to be those dyeswhich are not damaged at temperatures of 1l0-14'0 C. in aqueoussolutions whose pH value, measured at 20 C., is at least 8.5.

Reactive dyes of this type contain a substituent capable of forming achemical linkage with the substrate, e.g. a halogen atom, preferably achlorine or bromine atom,

' which is readily cleavable as an anion or a group which is readilycleavable as an anion, e.g. -OSO H, or a C-C multiple linkage readilycapable of addition. They may belong to the azo, metallized azo,anthraquinone, phthalocyanine or nitro series and contain, bound throughan oxygen or sulfur atom or through a monosubstituted or unsubstitutedimino group, at least one group, e.g. a dior tri-chloroor diortri-bromo-pyrimidyl group, a 2,4-dichloro-6-methyl-,2,4:dibromo-6-methyl-, 2,4 dichloroor 2,4 dibromo-pyrimidyl 5 methylenegroup, or a group bound through an oxygen or a sulfur atom or asubstituted or unsubstituted imino group and having the formula whereinsubstituted propionyl, a B-sulfatopropionyl or acrylyl group boundthrough a monosubstituted or unsubstituted imino.

group.

3,331,654 Patented July 18, 1967 r .ce

Dyes of the above type are described in the following patents: FrenchPatent 1,221,621 (dichloroand dibrornopyrimidylamino radical); BelgianPatent 578,742, Austrian Patent 214,546 (trichloroortribromo-pyrimidylamino radical); Belgian Patent 589,972 (2,4-dichloroor2,4 dibromo 6 methylpyrimidyl 5 methyleneamino radical); Belgian Patents559,944; 559,945; 560,734; 563,864; 560,791 to 560,795 (4-monoha1ogeno-1,3,5-triazinyl-2 radical substituted in the 6 position); BelgianPatents 565,279; 616,439; 576,104; 576,105; French Patent 1,203,580, andU.S. Patent 3,007,762 (,8- chloropropionylamino radical); BelgianPatents 565,279; 565,447; 572,862; 582,944; 583,050; 596,925; 617,961,and Swiss Patent 365,814 (acrylylamino radical).

The preferred reactive dyes are those which exhaust on cellulose to apractically acceptable degree from a bath containing a neutral salt.This is a general working rule for the textile colorist and signifiesthat dyes are used which exhaust onto cellulose in the presence of about20 grams or more of sodium sulfate or sodium chloride per liter of thedyeliquor.

The disperse dyes used can belong, for example, to the monoazo, disazo,anthraquinone, nitro, styryl or phthaloquinone series. They' form stabledispersions in the alkaline dyeliquors at the dyeing temperature andpossess good aflinity for polyester fibers and good light fastness onpolyester fibers. Their melting points are almost invariably higher than100 C., in general above 140 C. [Journal of the Society of Dyers andColourists 70, table on pages 69-71 (1954) and 74, page 339, Discussion(1958)]. Their solubility in Water at C. is generally, at the mostmg./liter, i.e. 1:10,000 [J oumal of the. Society of Dyers andColourists, 70, 69-71 (1954)] and preferably betweenabout 0.2 and 50 mg.liter. They contain no ionizing groups such -as',-COOH and SO H and nogroups which are readily converted into COOH or -SO H under the dyeingconditions, and also are free from groups which, if split 01f during thedyeing process,

would be detrimental to the aflinity for polyester fibers,

Can. Textile J., 76 (9) 49-59 (1959) Journal of the Society of Dyers andColourists, 70, 68-75 Journal of the Society of Dyens and Colourists,75, 141- American Dyestuff Reporter, 48, (14) 35-47 (1959) AmericanDyestuif Reporter, 49, (15) 600-605 (1960) Ullrnann, Enzyklopadie dertechnischen Chemie, volume 3, pp. 726-8 (1953), anthraquinone dyes;volume 4, pp. 128-9 (1953), aZo-dyes. I

French Patents 1,167,704, 1,177,337, 1,207,000, 1,220,- 194, 1,222,237,1,226,501, 1,237,149, 1,264,972,'1,280,- 998, 1,281,023, 1,291,988,1,261,580, and French additional Patents 75,125, 76,452, 78,167, azodyes French Patents 1,163,682, 1,218,936, 1,225,449, anthraquinone dyes,

French Patent 1,129,460, nitro dyes German Patent 677,641, styryl dyes;I

The basic fixing agents can be defined as compounds whose aqueous dilutesolutions at 20 C. show a pH-value of at least 8.5. Examples of suchbasic fixing agents are sodium, potassium or lithium hydroxide, sodiumor potassium carbonate, sodium or potassium bicarbonate, trisodiumphosphate or a sodium or potassium silicate in which the molecular ratioSiO :Na O or K 0 may vary from 1 :'l to 3.5: 1, e.g. a sodium orpotassium metasilicate or sodium or potassium water glass.

When sodium or potassium bicarbonate, is used, it is 3 decomposed intosodium or potassium carbonate and carbonic acid under the conditions ofdyeing, so that the pH-value in the dyeliquor is appreciably higher thanat room temperature.

4 and 3 parts of a dyeing preparation containing 1 part of sodiumdinapthylmethanedisulfonate, 0.5 part of sodium cetyl sulfate, 0.5 partof sodium sulfate and 1 part of a disperse dye mixture of ahydroxyphenyland an alkoxy- Dyeing is carried out at temperatures above100 C., 5 phenyl-1,5-dihydroXy-4,8 diaminoanthraquinone as dise.g. 110140 C., or preferably at 120-130 C., and at a closed in Example 43 fFrench Patent 1,218,936. liquor ratio of about 1:4 to 1:20, orpreferably 1:5 to 100 parts of a blended fabric consisting of 67 partsof 1:10. The amount of the basic fixing agent used is gov polyesterfiber (polyethyleneterephthalate), and 33 parts erned by the amount ofthe reactive dye employed and of cotton are entered into the bath at 40.The circulatmust be so calculated that the total amount of the halo- 1Oing bath is raised to 130 in 45 minutes, maintained at gen halideliberated during fixation is bound. It is prefthis temperature for 1hour and in the course of the next erable to employ the basic fixingagent in amounts slightly 20 minutes cooled to 60. The dyed fabric isrinsed in in excess over the mount theoretically ne es ary, o cold andhot water, soaped at the boil for 20 minutes in that the dyeing mediumremains of alkaline reaction up a 0.2% soap solution in dist Water,rinsed again in to the end of the dyeing process. Allowance must be made15 h t and C ld Water and dried. The blue dyeing is fast for the factthat at short liquor ratios, e.g. 1:4 to about to light, Washing, Water,perspiration and ru b 1:8, and with high concentrations of reactive dye,e,g, When the blue disperse dye mixture named above is reto on theWeight of the material, the amount of placed y one f the red disperse yof Examples 1, 2, basic fixing agent per liter must be greater than atme- 4 01 5 Of FI'CIlOh Patent 1,163,682 which have the 01- dium or longliquor ratios. Generally an addition of only mllla 0.5 to 2 grams sodiumcarbonate or trisodium phosphate or 0.5 to 1 gram sodium hydroxide perliter dyeliquor is O sufiicient, when dyeing is carried out at a liquorratio of ll 1 1:10. The dyed fibers or fabrics are rinsed in the usualway, washed if necessary with soap and sodium carbonate or with ananionic'or nonionic detergent andsodium carbonate, rinsed again anddried. The dyeings are of full H I depth and have good fastness tolight, sublimation, heat 0 0H (3) setting and dry cleaning, andexcellent fastness to water, washing at temperatures up to 100 C.,perspiration and rubbing. or by the violet disperse dye1-hydroxy-4-phenylamino- An important advantage of this process is thatat the anthraquinone [Am. Dyest. Rep., 49, 604, column 2 most only 5grams, or preferably 0.5-2 grams, of a basic (1960); Canadian TextileJ., 76 (9), 57 (1959), dye No. fixing agent per liter dyeliquor isnecessary in order to 21] or by one of the yellow dyes of the formulae-fix the reactive dye on the cellulosic fiber. On the other hand, it isvery surprising that polyester fibers can be dyed with disperse dyes inan alkaline dyeliquor without OH the dye being aggregated andprecipitated or adversely I 7 affected in some other way, sincepolyester fibers are C N-C 'N= normally dyed from a neutral or acidmedium, e.g. in 40 r the presence of benzoic acid or a mixture of sodiumor thophenylphenolate and an excess of ammonium sulfate or I ammoniumphosphate. [See J. Soc. Dyers and Col. 75 0113 146 (1959): Kirk andOthmer Encyclopedia of Chemical Tehn010gY, First Supplement Pages 2674i](Example 1 of French Patent 1,177,377)

In the following examples the parts and percentages are by Weight andthe temperatures in degrees centigrade.

Example 1 1110: V

A dyebath is prepared with 1000 parts of water, 2 parts NH of sodium3-nitrobenzene-sulfonate, 1 part of calcined O (D) sodium carbonate, 80parts of calcined sodium sulfate,

1 part of the dye of Example 2 of Belgian Patent 596,941 7 t whi h h sth f l 7 (Am. Dyest. Rep., 49, 604, column 2 (1960)), violet, O NH,violet-blue or green dyeings fast to light and Wet treat- V ments areobtained. 7 i By replacing the calcined sodium carbonate by the sameNaoas NN soiNa amount of calcined potassium carbonate, anhydrous lithiumcarbonate, calcined sodium or potassium metasilicate equally gooddyeings are obtained. 1 :IH o1 SIOZNB Example 2 i A dyebath is preparedwith 800 parts of water, 2 parts N C. g1 of sodium3-nitrobenzene-sulfonate, 05 part of calcined 55 trisodium phosphate, 60parts of calcined sodium sulfate,

| 0.7 part of the dye of Example 13 of Swiss Patent 361,- 01 (A) 066having the formula .Cl SO Na I I N.O\

H N: ama N C-C NaO S t SOsNa (E) and 3 parts of a dyeing preparationcontaining 1 part of lignin-sulfonate, 0.5 part of sodium cetyl sulfate,0.5 part of sodium sulfate and 1 part of the red disperse dye of Example4 of French Patent 1,163,682. 50 parts of cotton fabric and 50 parts ofpolyester fabric are entered into this dyebath. The bath is circulatedand raised to 130 in 30 minutes, maintained at this temperature for 45minutes and then cooled to 60 in the course of 20 minutes.

The dyed fabrics are rinsed in cold and hot water, soaped at the boilfor 20 minutes, in an aqueous solution containing 2 grams of sodiumdodecylbenzenesulfonate per liter, rinsed again in hot and cold water,and dried. The cotton fabric is dyed orange and the polyester fabricbluish-red; both dyeings have good light fastness and very good wetfastness properties.

When a blended fabric of cotton and polyester fiber in the ratio 1:1 isdyed in this bath, a reddish brown-orange shade is obtained.

Example 3 A dyebath is prepared with 1000 parts of water, 2 parts ofsodium 3-nitrobenzene-sulfonate, 2 parts of calcined sodium carbonate,60 parts of sodium chloride, 0.6 part of sodium2-[4'-(4"-chloro-6"-amino-1",3,5"-triazinyl-2"-amino)-2'-acetylamino-phenylazo-]-naphthalene 4,8- disulfonate[Belgian Patent 560,792, Example 2, and Collection of CzechoslovakChemical Communications 25, 2794 (1960)], and 1 part of a dyeingpreparation containing 35% 1-hydroxy-4-phenylamino-anthraquinone, 30%sodium dinaphthylmethane-disulfonate, sodium cetyloleylsulfate andsodium sulfate.

100 parts of a blended fabric of 67% polyester fiber and 33% cotton areintroduced into this bath at 40. The circulating bath is heated to 130in 45 minutes, maintained at this temperature for 30 minutes and cooledto 60 over the next 20 minutes. The dyed fabric is rinsed in cold andhot water, soaped at the boil for 20 minutes, rinsed again in hot andcold water and dried. The violet-grey dyeing is fast to light, washing,water, perspiration and rubbing.

Example 4 100 parts of a blended fabric of polyester fiber and cotton inthe ratio 2:1 are entered into a bath at 40 consisting of 1000 parts ofwater, 2 parts of sodium 3-nitrobenzeuesulfonate, 1 part of calcinedsodium carbonate, 60 parts of calcined sodium sulfate, 0.7 part ofsodium l-hydroxy 2 (4-acetylaminophenylazo) 6 [4"-chloro-6"- phenylaminol,3",5" triazinyl 2" amino] naphthalene-2,,2"',3-trisulfonate [BelgianPatent 560,973, Example 5; Collection of Czechoslovak ChemicalCommunications 25, 2794-5 (1960)] and 2 parts of the blue disperse dyepreparation used in Example 1, The circulating liquor is heated to 130in 45 minutes, maintained at this temperature for'30 minutes and cooledto 60 over the next 20 minutes. The dyed fabric is rinsed in cold andhot water, soaped at the boil for 20 minutes, rinsed again in hot andcold water and dried. The violet dyeing is fast to Wet treatments.

The sodium carbonate can be replaced by the equivalent amount ofanhydrous trisodium phosphate or by 0.5 part of sodium hydroxide, or by3 parts of a 34% sodium waterglass solution in which the molecular ratioof SiO :Na O is 3.321 or by 5 parts of a 30% potassium waterglasssolution in which the molecular ratio SiO :K O is 3.6:1.

Example 5 100 parts of a blended fabric of 67% polyester fiber and 33%viscose staple fiber are entered into a dyebath at 40 consisting of 700parts of Water, 2 parts of sodium 3-nitrobenzene-sulfonate, 80 parts ofcalcined sodium v6 sulfate, 0.5 part of sodium hydroxide, 0.6 part ofthe dye of formula n N-o soiNa on NHO /N o=o N=N l I NaOaS SOaNa(Belgian Patent 578,742, Example 10) and 2 parts of the blue dispersedye preparation used in Example 1. The circulating liquor is heated to130 in 3045 minutes, maintained at this temperature for 45 minutes andcooled to 60 in the next 15 minutes. The dyed fabric is rinsed with coldand hot water, soaped for 20 minutes at the boil, rinsed again in hotand cold water and dried. The violet dyeing obtained has very good wetfastness properties and good light fastness.

Equally good results are'obtained with 1 part of calcined sodiumcarbonate or 1 part of calcined trisodium phosphate in place of sodiumhydroxide.

Example 6 A dyebath is prepared at 40 with 1000 parts of water, 1 partof sodium 3-nitrobenzene-sulfonate, 1 part of c-alcined sodiumcarbonate, 50 parts of calcined sodium sulfate, 0.8 part of the dye ofthe formula nine 4,4',4",4'"

| NH-O O-CHz-CHa-Ol The dyed fabric is rinsed in cold and hot water,soaped at the boil for 20 minutes, rinsed again in hot and cold waterand dried. The green dyeing is :fast to light, washing, perspiration,water and rubbing.

In place of sodium carbonate, 1 part of anhydrous trisodium phosphate or0.5 part of sodium hydroxide or 2 parts of sodium or potassiumbicarbonate or 1.5 parts of potassium carbonate can be used.

Example 7 A dyebath is prepared with 1200 parts of water, 2 parts ofsodium 3-nitrobenzene-sulfouate, 0.6 part of sodium hydroxide, 60 partsof calcined sodium sulfate, 0.7 part of the dye (E) described in Example2 and 3 parts of the red dyeing preparation described in the sameExample 2. parts blended fabric of cotton and polyester fiber in theratio 1:2 are entered into this bath, which is circulated and raised toin 20 minutes, maintained at this temperature for 60 minutes and thencooled to 60 in the course of about 15 minutes.

The dyed fabric is rinsed in cold and hot water, soaped at the boil inan aqueous solution containing per liter 1 gram of a carboxymethylatedalkylpolyglycol ether and 1 gram of calcined sodium carbon-ate, rinsedagain and dried. A brown-orange dyeing having good light fastness andexcellent wet fastness properties is obtained,

The 0.6 part of sodium hydroxide can be replaced by 0.4-0.5 part oflithium hydroxide or 0.8-0.9 part of potassium hydroxide with equalsuccess.

7 Example 8 A dyebath is prepared with 1500 parts of water, 3 parts ofsodium 3-nitrobenzene-sulfonate, 2 parts of calcined sodium carbonate,60 parts of sodium chloride, 0.8 part of sodium2-[4'-(4"-chloro-6-amino-1,3",5"-triazinyl- 2 amino) 2' acetylaminophenylazo] naphthalene- 4,8-disulfonate [Belgian Patent 560,792, Example2, and Collection of Czechoslovak Chemical Communications 25, 2794(1960)], and 1.3 parts of a dyeing preparation containing 35%1-hydroxy-4-phenylaminoanthraquinone, 30% sodiumdinaphthylmethane-disulfonate, sodium cetyl-oleylsulfate and sodiumsulfate.

100 parts of a blended fabric of 67% polyester fiber and 33% cotton areintroduced into this bath at The circulating bath is heated to 140 in 30minutes, maintained at this temperature for 15 minutes and cooled to inabout 20 minutes. The dyed fabric is finished in the manner described inExample 7. The violet-grey dyeing is f t to li ht shi water,perspiration d bbi 2O ester fiber and 50% cotton are entered into thebath at E am le 9 40 The bath is circulated, reused to 125 in the course7 x of 30 minutes, and held for minutes at the same tem- A dyebath isprepared With 500 parts of water, 1 part perature. After cooling to60-70" the dyed fabric is reof sodium 3-nitrobenzene-sulfonate, 2 partsof sodium moved from the bath, rinsed with cold and with hot water,carbonate, 30 parts of sodium sulfate, 4 parts of the dye of 25 soapedat the boil for 15 minutes with an aqueous solution formula containing 2grams of sodium larurylpolyglycol ether sul- TABLE I) I (VI) Ex.Reactive Dye Amount Dispense Dye Amount Proce- Shade of Dyeing (parts)(parts) dure of on Blended Example Fabric 10.--.. Dye A (Example 1) 0.8Dye 0 (Example 1)- 0.40 1 Green. 11.- Cibaeron Brilliant Orange (31-130011. 0. 5 1-hydroxy-4-phe1iy1amino-anthraquinone 0. 35 4 Red-violet.

Czechosl. 25, 2794 (1960). Belgian Patent 578,742, Example 229 0. 6 DyeB (Example 1) 0. 35 1 D0. elgian Patent 578,742, Example 5. 0. 7 Dye D(Example 1) 0.7 1 Yellowish-green. French Patent 1,221,621, Example 2.0, 7 .--.do 0.7 1 Do. elgian Patent 589,972, Example 93.. 0.65 Dye 0(Example 1) 0. 4 1 Green. Belgian Patent 589,972, Example 123-. 0. 5Blue dye mixture of Example 1 0. 3 1 Blmsh violet. Belgian Patent589,972, Example 99.- 0. 8 French Patent 1,261,589, Example 19 0. 8 2Navy blue. French Patent 1,221,621, Example 30 0.5 1-%1hydroxyphenylazo)-4-pl1enylazo- 0.5 5 Orange.

enzene C.I. Disperse Yellow 23 (26070) German Patent; 1,058,467, Example7 6 French Patent 1,118,155, Example 1 4 6 Blue-vlplet. German Patent1,058,467, Example 3 do 2 Yellowlsh-green. Intermediate Product ofExample 1 of 5 0.1. Disperse Yellow 23 (26070) 4 6 Green. Belgian Patent616,439. 7 French Patent 1,203,580, Example 8 9 French Patent 1,237,149,Example 2 5 6 Red. (libgcrczrgfglue 3G-A Coll. Czechosl. 25, 7 FrenchPatent 1,167,704, Example 8. 5 2 Violet.

27 0 1 V Gilgagron I(Blacl BG-A Coll. Czechosl. French Patent 1,261,580,Example 17 9 Grey-black.

2 797 1960 Cibaoron Brown 3GR-A Coll. Czechosl. French Patent 1,291,988,Example 1 Brown.

.French Patent 1,211,086, Example 6 25,2798 (1960). Belgian Patent578,742, Example 197- French Patent 1,221,621, Example 91.

-. .do Belgian Patent 578,742, Example 1 French Patent 1,221,621,Example 1 Belgian Patent 578,742, Example 176 French Patent 1,225,281,Example 7 Belgian Patent 578,742, Example 1- Belgian Patent 578 742,Example 8 Dye E (Example 2) Cihacron Rublne R-A Coll. Czechosl.

25, 2795 (1960). Belgian Patent 578,742, Example 201 French Patent1,221,621, Example 91 Belgian Patent 578,742, Example 5 CibacronTurquoise Blue G-E 0011.

Czech. 25 2797 (1960). Dye A (Example 1)...

Gibacron Brilliant Red B-A 0011.

Czech. 25 2795 (1960). French Patent 1,211,086, Dye No. 18 of the Table.Belgian Patent 578,742, Example 87 Belgian Patent 578,742, Example 246French Additional Patent 75,033,

Example 1.

French Patent 1,268,684, Example 4 French Patent 1,268,684, Example 5.

French Patent 1,268,685, Example 2 000 000 0 0 0 0 000 0 00000000 00 w00 0 0 UH bhdi W0! U1 11. French Additional Patent 75,125,

Example 1. French Patent 1,281,023, Example 3 French Patent 1,291,988,Example Dye 0 (Example 1) Hydroxy-quinophthalone Can. Text. J.

Nitro-acridone Am. Dyest. Rep. 48 (14) p. 44 C01 1 1959. do

French Patent 1,291,988, Example 82 C.I. Disperse Yellow 23 (26070)French Patent 1,167,704, Example 8. N itro-acridone Am. Dyest. Rep. 48(14) French Patent 1,291,988 Example 82 Dye B (Example 1). DyeC (Example1)- Dye D (Example 1)...

Brownish violet. Orange-brown.

Brownish orange. Blue.

Brown.

Violet. 0range-ye1l0w. Yellow.

Violet.

Orange.

Red-violet.

Grey. Orange-yellow.

Yellowish-grcenx 7 e Reddish yellow. Green. 7

fate (about 3 ethenoxy groups) per liter, rinsed again and dried. Theobtained greyish black dyeing is fast to light and to wet treatments.

The above table contains further examples of dyeings which were obtainedaccording to the particulars given in Examples 1 to 9. The individualexamples are characterized by the nature and amount of the dyes used,the procedure according to one the Examples 1 to 9, and the shade of thedyeing obtained on a blended fabric of 67% polyester fiber and 33%cotton [columns (I) to V1] respectively. The parts of dye given in thetable are the amounts of pure dye that are required for dyeing 100 partsof blended fabric. The reactive dyes contain only small amounts ofsodium chloride or sulfate, Whereas the disperse dyes are employed inthe form of dyeing preparations consisting of 35% dye, 35% sodiumdinaphthylmethanedisulfonate, 15% sodium cetyl sulfate and 15% sodiumsulfate.

Having thus disclosed the invention what I claim is:

1. A process for dyeing a mixture of cellulosic and polyester fibers inone alkaline bath with reactive dye and with disperse dye, which dyesare stable to alkali at temperatures above 100 C., which processconsists of dyeing the mixture within the temperature range of from 110to 140 C. and at a goods-to-liquor ratio of from 1:4 to 1:20 in thepresence of a neutral salt and of at most 5 grams per liter of a basicfixing agent whose dilute aqueous solution possesses at 20 C. a pH-valueof at least 8.5.

2. A process according to claim 1, wherein the mixture of cellulosic andpolyester fibers is in the form of a blended fabric.

3. A process according to claim 1, wherein said temperature range isfrom 120 to 130 C.

4. A process according to claim 1, wherein the basic fixing agent is amember selected from the group consisting of sodium hydroxide, potassiumhydroxide, lithium hydroxide, sodium carbonate, potassium carbonate,sodium bicarbonate, potassium bicarbonate, trisodium phosphate, sodiummetasilicate, potassium metasilicate, sodium waterglass and potassiumwaterglass.

5. A process according to claim 4, wherein said basic fixing agentcomprises from 0.5 to 2 grams of anhydrous sodium carbonate per liter ofdyeliquor.

6. A process according to claim 4, wherein said basic fixing agentcomprises from 0.5 to 2 grams of anyhdrous trisodium phosphate per literof dyeliquor.

7. A process according to claim 4, wherein said basic fixing agentcomprises from 0.5 to 1 gram of sodium hydroxide per liter of dyeliquor.

8. A process according to claim 1, wherein the reactive dye employedcontains a radical selected from the group consisting ofdichloropyrimidyl, trichloropyrimidyl-, dichloropyrimidyl-methylene andmethyl-dichloropyrirnidylmethylene, the said radical being bound througha bridge 10 member selected from the group consisting of O, NH- andN(lower alkyl).

9. A process according to claim 1, wherein the reactive dye employedcontains a radical of the formula wherein y is a member selected fromthe group consisting of O-, NH and N(lower alkyl)-, and z is a memberselected from the group consisting of hydrogen, lower alkyl, sulfophenyland disulfopheny the said radical 'being bound through a bridge memberselected from the group consisting of O-, -NH and N(lower alkyl).

10. A process according to claim 1, wherein the reactive dye employedcontains a radical selected from the group consisting of,B-chloropropionyl, e-sulfatopropionyl and acrylyl, the said radicalbeing bound through a bridge member selected from the group consistingof -NI-I- and N(lower alkyl).

11. A process according to claim 1, wherein the reactive dye employed isselected from the group consisting of azo dye, metallized azo dye,anthraquinone dye, phthalocyanine dye and nitro dye.

12. A process according to claim 1, wherein the disperse dye employed isselected from the group consisting of monoazo dye, disazo dye,anthraquinone dye, nitro dye, styryl dye and phthaloquinone dye.

13. Mixtures of cellulosic fiber and polyester fiber dyed according tothe process claimed in claim 1.

14. Blended fabric of cellulosic fiber and polyester fiber dyedaccording to the process claimed in claim 2.

References Cited UNITED STATES PATENTS 3,093,437 6/19'63 Merian et al.8---21 3,100,132 8/1963 Jenny et al. 821 X 3,137,687 6/ 1964 Spoerri etal. 3,156,519 11/ 1964 Kallman et a1 855 3,164,436 1/ 1965 Altermatt 821X FOREIGN PATENTS 1,297,776 5/ 1962 France.

887,437 1/1962 Great Britain.

NORMAN G. TORCHIN, Primary Examiner.

J. HERBERT, Assistant Examiner.

UNITED STATES PATENT OFFICE GERTIFICATE ()F CORRECTION Patent N0 3 ,331,654 July 18 1967 Hans Husy It is hereby certified that error appears inthe above numbered patent requiring correction and that the said LettersPatent should read as corrected below.

Column 1, lines 57 to 63, the formula should appear as shown belowinstead of as in the patent:

H N C% l Hal C-y-z column 2, line 40, the last word should be or column4, lines 68 to 75, the extreme right-hand portion of the formula shouldappear as shown below instead of as in the patent:

c N C;"::::C

column 5 line 52 for "-2 ,Z ,3-trisulfonate [fBelgian Patent 560 ,973"read -2 ,2 ,3-trisulfonate [Belgian Patent 560 ,793 column 6, lines 30to 35, the indistinct word should be phthalocyanine columns 7 and 8, inthe table, fourth column, line 2 thereof, for "pheny amino-" read-phenylamin column 9, line 8, after "one" insert of Signed and sealedthis 6th day of August 1963.

(SEAL) Attest:

EDWARD M.FLETCHER,JR. EDWARD J. BRENNER Attesting Officer Commissionerof Patents

1. A PROCESS FOR DYEING A MIXTURE OF CELLULOSIC AND POLYESTER FIBERS INONE ALKALINE BATH WITH REACTIVE DYE AND WITH DISPERSE DYE, WHICH DYESARE STABLE TO ALKALI AT TEMPERATURES ABOVE 100*C., WHICH PROCESSCONSISTS OF DYEING THE MIXTURE WITHIN THE TEMPERATURE RANGE OF FROM 110*TO 140*C. AND AT A GOOD-TO-LIQUOR RATIO OF FROM 1:4 TO 1:20 IN THEPRESENCE OF A NEUTRAL SALT AND OF AT MOST 5 GRAMS PER LITER OF A BASICFIXING AGENT WHOSE DILUTE AQUEOUS SOLUTION POSSESSES AT 20*C. A PH-VALUEOF AT LEAST 8.5.